3-Phenoxypropyl 2-diazoacetate | 322478-31-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 3-Phenoxypropyl 2-diazoacetate
• 英文别名: 3-phenoxypropyl 2-diazoacetate
• CAS: 322478-31-9
• 化学式: C₁₁H₁₂N₂O₃
• 分子量: 220.228
• InChiKey: WWEAGKHHAODJFD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  16
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  37.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3-Phenoxypropyl 2-diazoacetate 在 dirhodium tetraacetate 作用下， 以 二氯甲烷 为溶剂， 以28%的产率得到
  参考文献：
  名称：

  Entropy-Controlled Asymmetric Synthesis. How Differential Activation Entropy Is Induced in Chiral Tethered Reactions

  摘要：

  [GRAPHICS]Kinetic measurements to determine effective molarities of intramolecular reactions using 2,4-pentanediol and related tethers showed that methyl groups on the tether accelerate the major diastereomeric process but decelerate the minor process. The efficient promotion of stereocontrol is suggested to be due to chiral perturbation of the reaction rate through the entropy term, The conformation of the encounter complex of the reagent and reactant moieties was deduced by stereochemical analysis of the intramolecular adducts.

  DOI：

  10.1021/ol006741m
• 作为产物：
  描述：

  3-Oxo-butyric acid 3-phenoxy-propyl ester 在 对甲苯磺酰叠氮 、 三乙胺 、 sodium hydroxide 、 水 作用下， 以 乙腈 为溶剂， 以58.9%的产率得到3-Phenoxypropyl 2-diazoacetate
  参考文献：
  名称：

  “Chiral Perturbation Factor” Approach Reveals Importance of Entropy Term in Stereocontrol of the 2,4-Pentanediol-Tethered Reaction

  摘要：

  The stereocontrol mechanism of the 2, 4-pentanediol (PD)-tethered reaction was studied in detail using a reaction system consisting of phenyl and rhodium carbenoid moieties. Different tethers were examined to analyze the effects of the methyl groups on the PD tether. Among the reactions with these tethers, the PD tether achieves an unmeasurably high stereoselectivity in a diastereomeric ratio of > 500. Another tether showing a high but measurable stereoselectivity in a ratio of 41 is mostly controlled by the entropy term. To clarify the role of the methyl groups on the chiral tethers, which are the origin of the stereocontrol, the "chiral perturbation factor" is introduced. This parameter is defined as the rate of a chiral reaction relative to that of an achiral reference reaction. By analyzing the temperature dependence of the chiral perturbation factors for different chiral-tethered reactions, high potentials of the PD-tethered reaction in its stereocontrol are concluded to be due to the entropy term.

  DOI：

  10.1021/jo025937s

文献信息

• Entropy-Controlled Asymmetric Synthesis. How Differential Activation Entropy Is Induced in Chiral Tethered Reactions
  作者：Takashi Sugimura、Kazutake Hagiya、Yasuhiro Sato、Takahiro Tei、Akira Tai、Tadashi Okuyama

  DOI：10.1021/ol006741m

  日期：2001.1.1

  [GRAPHICS]Kinetic measurements to determine effective molarities of intramolecular reactions using 2,4-pentanediol and related tethers showed that methyl groups on the tether accelerate the major diastereomeric process but decelerate the minor process. The efficient promotion of stereocontrol is suggested to be due to chiral perturbation of the reaction rate through the entropy term, The conformation of the encounter complex of the reagent and reactant moieties was deduced by stereochemical analysis of the intramolecular adducts.
• “Chiral Perturbation Factor” Approach Reveals Importance of Entropy Term in Stereocontrol of the 2,4-Pentanediol-Tethered Reaction
  作者：Takahiro Tei、Yasuhiro Sato、Kazutake Hagiya、Akira Tai、Tadashi Okuyama、Takashi Sugimura

  DOI：10.1021/jo025937s

  日期：2002.9.1

  The stereocontrol mechanism of the 2, 4-pentanediol (PD)-tethered reaction was studied in detail using a reaction system consisting of phenyl and rhodium carbenoid moieties. Different tethers were examined to analyze the effects of the methyl groups on the PD tether. Among the reactions with these tethers, the PD tether achieves an unmeasurably high stereoselectivity in a diastereomeric ratio of > 500. Another tether showing a high but measurable stereoselectivity in a ratio of 41 is mostly controlled by the entropy term. To clarify the role of the methyl groups on the chiral tethers, which are the origin of the stereocontrol, the "chiral perturbation factor" is introduced. This parameter is defined as the rate of a chiral reaction relative to that of an achiral reference reaction. By analyzing the temperature dependence of the chiral perturbation factors for different chiral-tethered reactions, high potentials of the PD-tethered reaction in its stereocontrol are concluded to be due to the entropy term.